Azo compounds containing fluorine



. Patented July. 25, 1950 AZO COMPOUNDS CONTAINING FLUORINE Joseph B.Dickey, Rochester, N. Y., sssignor to Eastman Kodak Company, Rochester,N. Y., a corporation oi New Jersey No Drawing. Application November 281945,

. Serial No. 631,469

7 Claims. 1 This invention relates to new azo compounds and theirapplication to the art of coloring.

I have discovered that the azo compounds having the general formula:

pounds. Depending upon their structure, the.

azo compounds of the invention possess application for the coloration oforganic derivatives of cellulose, nylon, wool and silk. They yielddyeings having excellentlight fastness.

. While my invention relates broadly to the azo compounds having theformula above given, it relates more particularly to those compounds vwherein R and R1 are monocyclic benzene nuclei and especially to thosecompounds wherein R and R1 are monocyclic benzene nuclei containing nonuclear sulionic acid or carboxylic acid group *and R contains a nitrogroup directly attached thereto in para position to the azo bond.

Both sulfonated and non-sulfonated compounds are included within thescope oi. my invention.

The nuclear non-sulionated compounds are of value for the coloration oforganic derivatives of cellulose, especially cellulose acetate rayon,and nylon and it is to these compounds and their application for thecoloration of organic derivatives of cellulose and nylon textilematerials that my invention is particularly directed. The nuclearnon-sulfonated compounds likewise possess some application for thedyeing of wool and silk. In general, the monoazo compounds wherein R andR1 are monocyclic benzene nuclei free from nuclear sulionic acid andcarboxylic acid groups and wherein R. contains a nitro group directlyattached thereto in para position to the azo bond are especiallyadvantageous for the coloration of organic derivatives of cellulose.

The nuclear sulfon'ated compounds of my invention have little or noutility for the coloration of organic derivatives of cellulose butpossess application for the coloration of wool and silk. Red, orange,orange-yellow, brownish-red, bluegreen, blue, rubine and violet shades,for example, can be obtained employing the dye compounds or theinvention.

It is an object 01' my invention to provide a new class of azo compoundssuitable for the coloration of organic derivatives or cellulose, ny-

lon, wool and silk. Another object o! my invention is to provide aprocess for the coloration of organic derivatives of'cellulose, nylon,wool and silk. A further object is to provide colored textile materialswhich are of good fastness to light and washing. A particular object isto provide a new class of nuclear ncn-sulfonated azo compounds suitablefor the coloration of cellulose acetate rayon. Another particular objectis to provide colored cellulose acetate textile materials which are ofgood tastness to light and washing. A still further object is to providea satisfactory process for the preparation or the azo compounds of myinvention. Other objects will appear hereinafter.

Typical organic derivatives of cellulose include the hydrolyzed aswellas theunhydrolvzed cellu-' lose organic acid esterssuch as celluloseacetate, cellulose formate, cellulose propionate, or cellu-.- losebutyrate and the hydrolyzed as well as the unhydrolyzed mixed organicacid estersoi cellu-'- lose, such as cellulose acetate-propionate,cellulose acetate-butyrate, and the cellulose ethers such as methylcellulose, ethyl cellulose, or benzyl cellulose. While the use orthecompounds ot my invention will be illustrated moreparticularly inconnection with the coloration of cellulose acetate rayon, a material towhich the invention is especially adapted, it will be understood that itapplies to the coloration of the other materials mentioned herein.

The azocompounds of my invention can be prepared by coupling diazotizedarylamines at the benzene and naphthalene series-diazotizedaminobenzothiazoles and diazotized aminoazobenzenes with a couplingcomponent of the benzene and naphthalene series containing a nuclearamino group. which is substituted with-an aliphatic hydrocarbon groupcontaining a trifluorinated carbon atom. I

It is to be here noted that the terms dlfluoroethyl, trifluoroethyl,triiiuoropropyl and trifluorobutyl wherever used herein mean2,2-difluoroethyl, 2,2.2-trifluoroethyl, 3,3,3-trifluoro-n-propyl and4,4,4-trifluoro-n-butyl, respectively.

The following examples illustrate the azo compounds of my invention andtheir manner of preparation:

trample 1.-1-(4-nitrophenplazo) 4 (N-p-hparoryethpi-N-trifluoroethvl)-aminobenzene OHgCHgOH 13.8 grams of p-nitroanillne are-dissolved in 150cc. of water and 25 cc. of 36% hydrochloric acid. The solution resultinak cooled to a temperature approximating -5 C. and the p-nitroaniline isdiazotized while maintaining this temperature by the addition. withstirrim, of a wator solution of 6.9 grams of sodium nitrite.

21.9 arms or N-p-hydroxyethyl-N-triiluoroethylaniline are dissolved in200 cc. of cold dilute aqueous hydrochloric acid and the diazoniumsolution prepared as described above is gradually added with stirring.Following the addition of the diazonium solution the mixture resultinais stirred, while maintaining a temperature of 0-l0 C.,- for aboutminutes after which the coupling reaction which takes place is completedby neutralizing the hydrochloric acid with sodium acetate. The dyecompound formed is recovered by filtration. washed with water and dried.It colors cellulose acetate rayon and nylon red shades.

trample 2.-1 (2 chloro-l-nitrophenvlaso) -2- methyl-#- (N- p -hpdroryethvl-lV-trifluoroeth- IU-aminobenzene CHrGFs 17.3 grams ofo-chloro-p-nitroaniline are dialotized and the diazonlum compoundobtained I B coupled with 23.3 grams of N-p-hydroxyethyl-N-trifluoroethyl-m-toluidine. The diazotization, coupling and dyerecovery operations can be carried out in accordance with the proceduredescribed in Example 1. The dye compound obtained colors celluloseacetate rayon and nylon rubine shades.

Example 3.--1-(4-nitrophenplazo) 2 chloro-l- (N flJWdrorpethpl-N-tflfluoroethpl) -aminobenzene 13.8 grams ofp-nitroaniline are diazotized and the diazonlum compound obtained iscoupled with 25.3 grams oiN-p-hydroxyethyl-N-trifluoroethyl-m-chloroaniline. The diazotization,coupling and dye recovery operations can be carried out in accordancewith the procedure described ln Example 1. The dye compound obtainedcolors cellulose acetate rayon and nylon orange shades.

Cl m CHIC K10 Is 1s 1 1 Example I. 1 (2.4 ditrifluoromethylphenplazo)-2-methyl-4- (lV-p-hudrorpethpl-N-trifiuoroethpl) -aminobenzene CHIC Itq ps omomon H! 22.9 grams of 2.4-ditrifluoromethylamllne are diazotiaedand the dlazonium compound obtained is coupled with 23.3 grams ofN-fl-hydroxyethyl- N-trifluoroetlwl-m-toluidine. The diazotization,coupling and dye recovery operations can be carried out in accordancewith the procedure described in Example 1. The dye compound obtainedcolors cellulose acetate rayon and nylon rubine shades.

Example 5.1 ((-acetophenplaso) -2-methpl-4- N-trifluoroethplaminobeneene13.5 grams of p-aminoacetophenone are diasotized and the diazoniumcompound obtained is coupled with 28.7 grams of N-trifluoroethyl-m+toluidine. The diazotization, coupling and dye recovery operations canbe carried out in accordance with the procedure described in Example 1.The dye compound obtained colors cellulose acetate rayon and nylonorange shades.

Example 6.1 (6-chloro-2,4-dinitrophenylazo)- 2 acetamino-5-methorp-4-(N-fln-dihpdrmpropfll-N-triflaoroethpl) -aminobeneene -com (A) 21.8grams of 6-chloro-2,4-dinitroaniline are dissolved in 220 cc. of hotglacial acetic acid and the resulting solution is rapidly cooled to roomtemperature.

(B) 7 grams of sodium nitrite are dissolved in 53 cc. of sulfuric acid(sp. gr. 1.83) by heating the mixture to 10 C., and the resultingsolution is then cooled to 15-20 C.

Solution (A) is added with stirring to (B) N/CHrCII cmcnononm over aperiod of 30 minutes, while maintaining a temperature of 15-20 C. andthe mixture re-- Example 7.1 (2,6-dichloro-4-nitrophenplaso)- 2 chloro4.-N,N-ditriflu0r0p1'om!l-aminobenzene diamtization, coupling and dyerecovery operations are carried out in accordance with the proceduredescribed in Example 6. The dye compound obtained colors celluloseacetate rayon and nylon violet shades.

trample 17.1- (l-nltrophenylezo) -4- (MN-dimjluoroethyl) -aminobenzene13.8 grams of p-nitroaniline are diazotized and coupled with 25.7 gramsof N,N-ditrifluoroethylaniline. The diazotization, coupling and dyerecovery operations can be carried out in accordance with the proceduredescribed in Example 1. The dye compound obtained colors celluloseacetate rayon and nylon orange shades.

Example 18 01110 HIGH CHaCF:

Example 19 19.4 grams of 2-amino-5-ethoxybenzothiazole are diazotizedand coupled in an acid medium with 22.5 grams ofN-trifluoroethyl-a-naphthylamine. The dye compound obtained colorscellulose acetate rayon and nylon rubine shades.

Example 20 omomon CHQC F| 19.! grams of p-aminoazobenzene are diazotizedand the diazonium compound obtained is coupled in an acid medium with23.3 grams of N-p-hydronethyl N trifluoroethyl m toluidine.'

The dye compound obtained colors cellulose acetate rayon and nylon redshades.

Example 21 cHlC more! O HIC Fr out in accordance with the proceduredescribed 15 in Example 1. The dye compound obtained colors celluloseacetate rayon, nylon and sill: yellowishorange shades.

Example 22 13.8 grams of p-nitroaniline are diazotized and the diazoniumcompound obtained is coupled in a slightly acid medium with 24.1 gramsof 5-hy- I droxy 1 trifiuoroethylaminonaphthalene. The dye compoundobtained colors cellulose acetate rayon, nylon and silk violet shades.

Example 23 NOy-QN: N-omo m 21.8 grams of l-amino-2-sulfonic-4nitrobenzene are diazotized in known fashion and thediazonium compound obtained is coupler? in an acid medium with 22.5grams of -N-trlfluoroethyla-naphthylamine. The dye compound obtainedcolors silk, wool, and nylon rubine shades.

Example 24 sour Example 25 SOiH H Hols-glue gar-0111c F:

30.1 grams of 1-amino-2,4'-disulfonicnaphthalene are diazotized and thediazonium compound obtained is coupled in an acid medium with 22.5 gramsof N-trifluoroethyl-a-naphthylamine. The dye compound obtained colorssilk, wool and nylon violet shades.

The following tabulation further illustrates the compounds includedwithin the scope. of my invention together with the color they produceon cellulose acetate rayon and nylon. The compounds indicated below maybe prepared by diazotizing the amines listed under the heading Amine andcoupling the diazonium compounds obtained with the compounds specifiedin the column entitled Coupling Component. The diazotization andcoupling reactions may, for example, be carried out following thegeneral procedure described in the foregoing examples:=

Tabulation A-Continued- Amine Coupling Component Color a ill oride C011lilig Com cents 1 to 45 Orange to rubine. 2 t-mmmm qmi Reddish-brown tod brgwnish-rubine. o-bromo-i-chloro-i-nitroanilin 0--.- (Lbiiuoto-fl-chloroi-nitroaniline .-dop phthylamine Yellow to orange.

l-cmino-2,4-dinitrona Orange to violet.

l-unino-t-h droxynaphthalenm- Orange to rubine.

inouo nzene Do.

-chloro-4-nitromincszobenzen Do. hmino o-ethoxy zothiazole .-do.l-unino-s-methoxy iatoleu d0 Do.

The compounds indicated in the following ponents used in theirmanufacture is described tabulation can be prepared following theprohereinafter. oedure described in the examples given hereis Thebenzene coupling components of the ininbeiore. They color celluloseacetate rayon and vention can be prepared by reacting a chloronylon thecolors set forth. benzene compound with a trifluoroalkylamine. If

Tabulation B Amine Coupling Component Color pin-can in (1)-hydroxy-l-trifluoroethylaminonaphtbalene Violet. p. Deaf a (2)o-hydroxy-l-triiiupro pylaminona htbalene..... Do. Do (3)Z-ethoxy-l-trifluoroet ylarninonapht alene Rubine. Do (4131-10111oro-ii-hydroxy-l-trifluoroethylaminonnph- Violet.

one. Do (5) ii bromo-ii-hydroxy-1-trilluorobutylaminonaph- Do.

ene. p-nmin n Coupling Components 1-6 above Red.I-hydroxy-d-uitroaniline ..dO Violet.. fl-chioro-d-nitr do Do.o-aminophenylmethylsuii d0 Red. o-N-othylsuliamyl-zbdinitroanilin doBlue. p-aminoazobentene fin Reddish-violet. u-na hthylamine rln Orange.2,4-fnitrmu-naphthylamine .J. .-do. Blue. d-ethoxybenzothlazole d0Violet. 5-methoxybenzotbiazole-..-. do Do.

Similarly, the compounds indicated in the foldesired, a catalyst for thereaction such as powlowing tabulation can be prepared following theprocedure described in the examples given hereinbeiore. They color silk,wool and nylon textile materials red, orange, orange-yellow, rubine anddered copper and cuprous oxide can be employed. The benzene couplingcompounds of the invention can also be prepared by reaction betweenanaminobenzene compound and a trifluoroalkanol violet shades, forexample. 4" 1n the presence of a metallic hydrogenation cata- Tabulation0 Amino Coupling Component i mino-i-nitro-z-sulionicbenzene (l)N-triiiuoroethylaniline.

Do (2)N-trifluoroethyl-N-fl-hydroxyethylaniline. Do (3)N-trifluoroethyl-N-fi-hydroxyethyl-m-toluidine. Do 4)N-triiluoroethyl-N-4,5-dihydroxyamylaniline. Do (5)N,N-ditriiiuoroethylaniline. Do (6)N-trifluoropropyl-N-B-hydroxyethylaniline. Do-.)N-trifluoropropyl-N-firy-dihydroxyprc yl-m-toluidine. Do 8)5-hydroxy-l-trifiuoroethylaminonapht ene. Do. (9)l-trifluoroethylaminonaphthalene. p-sulianilic acid. Cougling Components1-9 above. l-nmino-2-chloro-4-sulfonicbenzene 0.l-amino-2,4-disulionicbenzene Do. l-amino-2-sulionicnaphthalene.. Do.l-nmino-Z-hydroxyA-sulionicna ht Do. Q-naphthylamine-S-sulionic aci Do.

1-amino-3,8-disulfonicnaphthalene, Lamina-4,8-

disuii'onicnaphthalene and l-amino-S-hydroxy- 'l-sulfonicnaphthalene.

In order that my invention may be clearly understood the preparation ofthe coupling comlyst such as Raney nickel and other nickel catalysts, acobalt catalyst and copper chromite. A still further method by which thecoupling compounds of the invention can be prepared is by reactionbetween anaminobenzene compound and a trifluoroalkyl halide in thepresence of an acid binding agent. Acid binding agents that can be usedinclude, for example, sodium carbonate, potassium carbonate, sodiumhydroxide, potassium hydroxide, sodium bicarbonate, potassiumbicarbonate and barium hydroxide. Each of these methods of preparationis illustrated hereinafter. Trifluorcalkylamines that can be used in thepreparation of the compounds of my invention include, for example,2,2,2-trifluoroethylamine (CECHzNHz) 8,8,3 trlfluoropropylamln(CFsOHaCEaNHa). 4,4,4 trifluorobutylamine (CFsCHaCHeCHaNHa),

5,5,5-trifluoroamylamine (CFaCHzCHaCmCHzNm) and8,6,6-triiluorohexylamine (CFaCI-IaCHaCHzCHaCHzNHz) Trinuoroalkylhalides that can be employed include, for example, CFaCHaCl,CF'sCl-IzBr, CFaCHaI, CFaCHaCHzCl and CFeCHzCHzCHaCl. Triiluoroalkanolcompounds that. can be employed include.

for example, 2,2,2-trifluoroethanol' .(CFaCHaOH) and CFaCHOHCHs. V

L Erample A.-N-(2,2,2-trifluoroeth1!l)aniline O-N-OHsO If:

- 28 grams of chlorobenzene, 100 grams of 2,2,2- triiluoroethylamine(CFaCHaNHa). 800 cc. of water, 0.25 gram of copper powder and 0.25 gramoi. cuprous oxide are heated together in a copper lined shakingautoclave at 220-225' C for 24 hours with shaking. when cool, thecontents of the autoclave are removed and extracted with benzene. Afterdrying the benzene extract is fractionally distilled under reducedpressure to recover N-(2,2,2 -trifiuoroethyl)-aniline and unreacted2,2,2-trifluoroethylamine.- N-(2,2,2-trifluoroethyl) -aniline isacolorless liquld'boiling at 135-136/ 12 mm.

" Using the procedure described in Example A and employing the properchlorobenzene com-.

pound, the following compounds are readily prepared:N-trifluoroethyl-o-chloroaniline N-trifluoroethyl-o-toluidineN-trifiuoroethyl-m-toluidine N-triiiuoroethyl-o-ethylanilineN-trifluoroethyl-z-methoxy-5-acetaminoaniline By the use of3,3,3-trifluoropropylamine (CFaCHaCHrNHa) 4,4,4 trifluorobutylaminecracmcmcnmm),

5,5,5-trifluoroamylamlne (CFaCHzCHaCI-IzCI-IaNHa) and6,6,6-trifluorohexylamine I (cracmcmcmcmcmm)N-(3,3,3-trifluoropropyl)-2-methoxy-5 methylanilineN-(3,3,3-trifluoropropyl) -m propionylaminoaniline N-(4,4,4-trifluorobutyl) -m-tluidine N-(5,5,5-trifiuoroamyl) o-anisidineN-(6,6,6-trifluorohexyl)-m-anisidine Example B.-N-(2,2,2 trifluqroethvl)-m-toluidfne 4': grams ,of m-toluidine, 80 grams of2,2,2-trifluoroethanol and 5 grams of Raney nickel are heated togetherin a shaking autoclave for.

hours. when cool, the contents of the autoclave are removed and filteredto remove nickel and the filtrate is fractionated under reduced pressure(6 mm., for example). N-(2.2,2-triiluoroethyl) -m-toluidine is obtainedin a good yield and boils at HIS-147! mm.

trample C'.-N-(2,2,2-trifluoroisoprml) -manieidine This compound isprepared by reacting 55 grams of m-anisidine with 90 grams ofcrooner-1cm in accordance with the procedure described in Example B.

Example D.-N (2,2,2-trifluoroethul) -o-chloroaniline 17 grams of2,2,2-triiluoroethylbromlde, 13.8 grams of o-chloroaniline and 6 gramsof sodium carbonate are placed in a suitable reaction vessel and heatedunder refluxing conditions until car-- bon dioxide ceases to be evolved.Upon cooling the reaction mixture is extracted with ethyl alcohol andthe ethyl alcohol extract is fractionated under reduced pressure (2 mm.,for example) to give a good yield of N-(2,2,2-trliluoroethyl)-o-'chloroaniline.

Example E.N,N-ditri'fluoroethulaniline 17.5 grams ofN-trifluoroethy1-n-toiuidine, 1'! grams of trifluoroethylbromide andgfigrams of sodium carbonate are placed in a suitable reaction vessel andheated under refluxing conditions until carbon dioxide ceases to beevolved. The reaction product is extracted with ethyl alcohol and 40 theethyl alcohol extract is fractionated under reduced pressure (5 mm., forexample) to give a good yield of N,N-trifluoroethylaniline.

Example I F. N-trifluoroethyl-N-dtfluoroethylaniline This compound isobtained by reacting N-trifluoroethylaniline with2,2-difluoroethylbromlde (CI-IFzCHzBr) in accordance with the proceduredescribed in Example E.

Example G.- N ,s methozyethvl N trifluoro ethylaniline This compound canbe obtained by reacting N- p-methoxyethylaniline with2,2,2-trifluoroethylbromide in accordance with the procedure describedin Examples D and E.

Using the procedure of Examples B and C th following compounds arereadily prepared:

00 N-triiluoroethyl-o-anisidineN-trifluoroethyl-2-methoxy-5-methylanilineN-2,2,2-trifluoroisopropylaniline N-2,2,2-trifluoroisopropyl-m-toluidineN-2,'2,2-trifluoroisopropyl-o-chloroaniline noN-2,2,z-trifluoroisopropyl-m-chloroanilineN-2,2,2-trifluoroisopropyl-o-anisidine Similarly using the procedure ofExamples 19, 11,1 and G, the following compounds are readilyprepared:

N,N-ditriiiuoroethyl-m-toluidine N,N-ditriiluoroethyl-m-anisidineN,N-di- (3,3,3-trifluoropropyl) -m-chloroaniline N,N-di-(4,4,4-trifluorobutyl) -aniline 3o N,N-ditrifluoroethyl-m-bromoaniline15 'N,N-ditriiluoroethyl-m-fluoroaniline N-triiluoroethyl-N-(3,8,3-trifluoropropyl) -aniline N-triiluoroethyl-N-(4,4,4-tritluorobutyl-m toluidineN-2,2-diiluoro-n-propyl-N-triiluoroethylanilineN-2,2-dliluoro-n-propyl-N-triiiuoroethyl-mtoluidlne N-2,2,-diiluoron-propyl-N-3,3,3-trlfluoropropylanilineN-3,3-diiluoropropyl-N-triiluoroethylaniline N-3,3-dliluoropropyl-N-triiluoroethyl-mtoluidlneN-3,3-difluoro-n-butyl-N-triiluoroethylanilineN-3,3-diiluoro-n-butyl-N-tritluoroethyl-mtoluidlne8-3.3-difluoro-n-butyl-N-3.3,3-trifluoropropylanilineN-3,3-difluoro-n-butyl-N-3,3.3-triiluoropropylm-toluidineN-3,3-diiluoro-n-butyl-N-4,4,4-triiluorobutylaniline8-3.3-difluoro-n-butyl-N-4,4,4-triiiuorobutyl m-toluidineN-3,3-difluoro-n-butyl-N-triiluorobutyl-2 methoxy-fi-methlyanilineN-p-ethoxyethyl-N-triiluoroethylaniline N-p-methoxyethyl-N-(4,4,4-triiluorobutyl) aniline Compounds containing the2,2-diiluoro-n-propyl (-CH:CF2CI-la), 3,3-difluoropropyl (CH:CH-.-CHF:)

and 3,3-diiluoro-n-butyl groups (-CHzCHsCF'aCHa) are prepared byreacting an N-trifiuoroalkylaniline compound with an equivalent grammolecular weight of CI-hCFzCHzC], ClCHsCHzCHF: or Brcrncmcnra andCI-hCFzCI-BCHzCl, respectively; in accordance withthe general proceduredescribed in Examples E and F.

Example H.N-p-hydrozyethyl-N-trifiuoroethwlaniline 1'? grams ofN-triiluoroethylaniline, 5 grams oi ethylene oxide and 50 cc. of dioxaneare heated together with stirring in an autoclave at 180 C. for sixhours. Upon cooling, the reaction mixture is removed from the autoclaveand distilled under reduced pressure. N-p-hydroxyethyl-N-trifluoroethylaniline hailing at 1B5-l6'l/18 mm, is obtained.

Using the procedure described in Example H and employing the properalkylene oxide, (trimethlyene oxide, propylene oxide, glycidol andmethyl glycidol) the following compounds are readily prepared:

N-y-hydroxypropyl-N-trifluoroethylanilineN-fl-hydroxypropyhN-triiluoroethylaniline N1,)-dihydroxypropyl-N-trifluoroethylanllineN-4,5-dihydroxyamyl-N-trifluoroethylanilineN-4,5-dihydroxyamyl-N-trifluoroethyl-mtoluidine N-p-methyl4,1-dihydroxypropyl-N-trifluoroethylaniline N-p-methyl-8,7-dihydroxypropyl-N-trii'luoroethyl-m-toluidine N-p,-dihydroxypropyl-N-trifluoroethyl-mbutoxyanilineN-flJ-dihydroxypropyl-N-3,3,3-trifluoropropylm-toluidineN-fln'-dihydroxypropyl-N-4,4,4-triiluorobutylaniline Where a p-dihydroxypropyl group or other 75 group which will decompos ii thecompound is attempted to be distilled is present, the reaction mixtureis removed from the reaction vessel, illtered, it necessary, and thesolventmedium removed by distillation under reduced pressure leavin thedesired product as the residue of the distillation.

Example L-N-p-hydroxyethyi-N-trifiuoroethylm-chloroaniline 20.9 grams ofN-trinuoroethyl-m-chloroaniline,

5 grams of ethylene oxide and 50 cc. of dioxane are heated together withstirring in an autoclave at 180 C. for six hours. Upon cooling, thereaction mixture is removed from the autoclave and distilled underreduced pressure. A good yield ofN-p-hydroxyethyl-N-triiluoroethyl-m-chloroaniline is obtained,

Example J.--N-p,1-dihudroxupr0pul-N-triflmro=ethyl-2-methoxy-5-acetaminoaniline 26.2 grams ofN-trifluoroethyl-2-methoxy-5- aeetamlnoanlline and 10.6 grams of sodiumearbonate are mixed together and heated with stirring in a suitablereaction vessel in an atmosphere of nitrogen to 0. Then 12 grams ofglycerolchlorohydrin (CICHzCHOHCHaOH) are added drop by drop withstirring over a period oi three hours, while maintaining the temperatureat 140? C. When carbon dioxide ceases to be evolved. the reactionmixture is extracted with acetic acid and the acetic acid extract iscarefully fractionated under reduced pressure to remove the acetic acid.N-p,/-dihydroxypropyl-N trifluoroethyl- 2-methoxy-5-acetaminoaniline isobtained as a dark, viscous product and is stored in a stoppered bottle.

Where the intermediate is to be used as a coupling component in thepreparation of azo dyes, the fractionation operation may be omitted andthe acetic acid extract stored and used as such. If desired, thereaction mixture can be extracted with butyl alcohol and the desiredproduct recovered by removing the butyl alcohol by distillation orevaporation' Example K.N-p-hydroxyethyl-N-trifluoroethyl-m-toluidz'ne18.9 grams of N-trifluoroethyl-m-toluidine, 5 grams of ethylene oxideand 50 cc. of dioxane are heated together with stirring in an autoclaveat C. for 6 hours. Upon cooling, the reaction mixture is removed fromthe autoclave and distilled under reduced pressure (2 mm., for example).A good yield of N-p-hydroxyethyl-N- triiluoroethyl-m-toluidine isobtained. I

The process described in Example J is broad ly applicable. In place ofthe chlorohydrin used in the example ethylene chlorohydrin, trimethylenechlorohydrin, B-methyl-BJ-dihydroxypropylchlorohydrin, propylenechlorohydrin and 1-chloro-2,3,4-trihydroxybutane, fo example, can beused to obtain coupling compounds of the invention. a

- Using the procedure described in Examples H, I, J, and K, thefollowing compounds, for example, are readily prepared:

N-trifluoroethyl-N s hydroxyethyl m acetminoanilineN-trifluoroethyl-N-p-hydroxyethyl-2 methoxy- 5-methylanilineN-trifluoroethyl-N-p-hydroxypropylanilineNf-trifluoroethyl-N-p-hydroxypropyl-m-toluidineN-triiluoroethYI-N-BJ-dihydroxypropyl-m-toluidine N;-trifluoropropyl-N-phydroxyethyl-m-toluidine N-trifluoropropyl-N-B.Y-dihydroxypropylanilineN-trifluoropropyl-N-2,3,4 -trihydroxybutyl methylanilineN-trifluorobutyl-N-p-hydroxyethylanilineN-trifluorobutyl-N-p-hydro1wethyl-m-to1uidineN-trifiuorobutyl-N-4,5-dihydroxyamylanilineN-5,5,5-trifluoroamyl-N-p-hydroxyethylaniline N-5,5,5-trifiuoroamyl-N-..'Y-dihydroxypropylmtoluidiue N-6,6,6-trifluorohexyl-N aniline ExampleL.Methyl ester of N-s-carbomyethyl- N-trifluoroethylanilin 5. 'Y i ydrop py 17.9 grams of the methyl ester of N-fi-carboxyethylaniline, 17grams of triiluoroethylbromide and 6 grams of sodium carbonate areplaced in a suitable reaction vessel and heated under rev fluxingconditions until carbon dioxide ceases to be evolved. Upon cooling, thereaction mixture is extracted with ethyl alcohol and the ethyl alcoholextract is fractionated under reduced pressure, 5 mm., for example, togive a good yield of the methyl ester ofN-p-carboxyethyl-N-trifluoroethylaniline.

Using the procedure described in Example L, the following compounds arereadily prepared:

Methyl ester of N-p-carboxyethyl-N-trifluoroethyl-m-toluidine Methylester of N-p-carboxyethyl-N-trifluoroethyl-m-anisidine Methyl ester ofN-p-carboxyethyl-N-3,3,3-trifluoropropylaniline Methyl ester ofN-p-carboxyethyl-N-4,4,4-trifluorobutylaniline ExampleM.--N-y-ketobutylaniline-N-trifluoroethylaniline 16 grams ofN-y-ketobutyl, 17 grams of trifluoroethylbromide and 6 grams of sodiumcarbonate are placed in a suitable reaction vessel and heated underrefluxing conditions until carbon dioxide ceases to be evolved. Uponcooling, the

reaction mixture is extracted with ethyl alcohol 8 ExampleN.N-p-cyanoethvl-N-trifluoroethylaniline 20 grams of N trifluoroethylaniline. 30 grams of acrylonitrile and 2 cc. of sulfuric acid areplaced ina suitable reaction vessel and heated on a steam bath forseveral weeks. The sulfuric acid is then carefully neutralized by theaddition of sodium hydroxide and the reaction mixture is fractionatedunder reduced pressure; A good yield ofN-s-cyanoethyl-N-trifluoroethylaniline is obtained.

Using the procedure described in Example N, the following. compounds arereadily prepared:

N-p-cyanoethyl-N-trifluoroethyl-m-toluidineN-p-cyanoethyl-N-3,3,3-trifluoropropylaniline N-fi-cyanoethyl-N-4,4,4trifluorobutyl-m-toluidine The N-trifluoroalkylnaphthylamine couplingcomponents of the invention can be prepared by the general methodsdescribed in connection with the N-trifluoroalkylaniline couplingcomponents. Thus u-naphthylamine can be reacted with 2.2.2-trifluoroethanol and CFsCHOHCHa, respectively.

in accordance with the procedure described in Examples B and C to obtainN-trifluoroethyl-n naphthylamine and N-(2,2,2-triiluoroisopropyl)-a-naphthylamine, respectively. a-Naphthylamine andI-amino-5-hydroxynaphthaIene, for example; can be reacted with2,2,2-trifluoroethylbromide in accordance with the procedure describedin Example D to obtain N-trifluoroethyla-naphthylamine and5-hydroxy-1-trifluoroethylaminonaphthalene, respectively. Alsoachloronaphthalene can be reacted with a trifluoroalkylamine inaccordance with the procedure described in Example A to obtainN-trifluoroalkyl a-naphthylamine. Thus N-trifluoroethyl-a-naphthylamine,N trifluoropropyl a naphthylamine, N- trifluorobutyl-a-naphthy'lamine,for example, can be prepared by reacting a-chloronaphthalene with 22,2-trlfluoroethylamine, 3,3,3-trifluoropropylamine and4,4,4-trifluorobutylamine, respectively.

From the foregoing it is believed that the manner of preparation of theN-trifluoroalkylnaphthylamine compounds of my invention is clear tothose skilled in the art to which this invention is directed and nofurther description of their preparation is thought necessary.

The azo compounds of my invention can be employed for the coloration ofthe materials named herein by the well known methods, employed by thoseskilled in the art, for the colora- 5 tion of these materials.

and the ethyl alcohol extract is fractionated under reduced pressure (3mm., for example) to give a good yield of N-v-ketobutyl-N-trifluoro- Lethylaniline.

Using the procedure .described in Example M, the following compounds arereadily prepared:

- N-'yketobutyl-N-trifluoroethyl-m-toluidine-N-Y-ketobutyl-N-trifluoroethyl-2-methoxy 5 acetaminoanilineN-p-ketopropyl-N-trifluoroethylanilineN-p-ketobutyl-N-trifluoroethylaniline N-trifluoroalkylaminobenzenecompounds are described and claimed in my copending application SerialNo. 624,942, filed October 26, 1945. Reference may be had to thisapplication for additional information concerning the preparation ofthese compounds.

N-difluoroalkylaminobenzene compounds are described and claimed in mycopending application Ser. No. 624,943, filed October 26, 1945.

5 Reference may be had to this application for additional informationconcerning the preparation of these compounds.

Azo compounds containing an amino group which is substituted with analiphatic hydrocarbon group containing a difluorinated carbon atom aredescribed and claimed in my copending application Serial No. 631,468,filed November 28, 1945.

.I claim:

1. An azo compound, free from sulfonic and carboxylic acid groups,

formula wherein R represents a mono nitrated monocyclic benzene nucleusand whereinsaid nitro group is in para position to the azo bond, Xrepresents a member selected from the group consisting of a2,2,2-trifluoroethyl group, a 3,3,3-trifluoro-npropyl group and a4,4.4-trifluoro-n-butyl group,

having the general Y represents a member selected from the groupconsisting of a hydrogen atom and a hydroxyalkyl group having 2 to 5,inclusive, carbon atoms and Z represents a member selected from thegroup consisting of a hydrogen atom, a chlorine atom and a methyl group.

2. An azo compound having the general formula:

wherein R represents a trifluorinated straight chain alhl group havingtwo to four carbon atoms and wherein said fluorine atoms are on a singlecarbon atom and R1. represents a hydroxyalkyl group having 2 to 5,inclusive, carbon atoms.

3. An azo compound having the general formula:

.wherein R represents a trifluorinated straight chain. allwl grouphaving two to tour carbon atoms and wherein said fluorine atoms are on asingle carbon atom and R1 represents a hydroxyalbl group having 2 to 5,inclusive, carbon atoms.

4. An azo compound having the general formula:

20 wherein X represents a halogen atom, R repre sents a trifluorinatedstraight chain alkyl group having two to four carbon atoms and whereinsaid fluorine atoms are on a single carbon atom and R1 represents ahydroxyalkyl group having 2 to 5, inclusive, carbon atoms.

5. The azo compound having the formula:

summon 6. The azo compound having the formula:

CHaC Fl 7. The azo compound having the formula:

CHaC Fl 1 CHzCHaOH JOSEPH B. DICKEY.

REFERENCES CITED The following references are. of record in the file ofthis patent:

UNITED STATES PATENTS OTHER REFERENCES Gilman, Organic Chemistry, 2nded., pp. 962,

m 963 (1943), pub. John Wiley 8: Sons, New York.

1. AN AZO COMPOUND, FREE-FROM SULFONIC AND CARBOXYLIC ACID GROUPS, HAVING THE GENERAL FORMULA: 